Additive formulation suitable for antistatic modification and improving the electrical conductivity of inanimate organic material

Abstract

An additive formulation suitable for antistatic modification and improving the electrical conductivity of inanimate organic material, consisting essentially of (A) from 1 to 50% by weight of an olefin-sulfur dioxide copolymer, (B) from 1 to 50% by weight of a compound which comprises one or more basic nitrogen atoms and has at least one relatively long-chain linear or branched hydrocarbon radical having at least four carbon atoms or an equivalent structural element which ensures the solubility of component (B) in the inanimate organic material, (C) from 0.1 to 30% by weight of an oil-soluble acid and (D) from 1 to 80% by weight of a high-boiling organic solvent which consists of one or more molecule types, where at least 80% by weight of these molecule types have a boiling point of more than 150 C. at standard pressure,
where the sum of all components adds up to 100% by weight.

Claims

1. An additive formulation suitable for antistatic modification and improving the electrical conductivity of inanimate organic material, consisting essentially of (A) from 1 to 50% by weight of an olefin-sulfur dioxide copolymer, (B) from 1 to 50% by weight of a compound which comprises one or more basic nitrogen atoms and at least one linear chain or branched hydrocarbon radical having at least four carbon atoms, (C) from 0.1 to 30% by weight of an oil-soluble acid and (D) from 1 to 80% by weight of an organic solvent which comprises at least 80% by weight of a mixture of aromatic hydrocarbons having from 9 to 20 carbon atoms, where at least 80% by weight of the organic solvent compounds have a boiling point of more than 150 C. at standard pressure, wherein the sum of components (A) to (D) is 100% by weight, the compound (B) does not comprise a free hydroxyl group, and a flash point of the additive formulation is not less than 62 C.

2. The additive formulation according to claim 1, consisting essentially of (A) from 10 to 30% by weight of component (A), (B) from 10 to 30% by weight of component (B), (C) from 2 to 15% by weight of component (C) and (D) from 40 to 78% by weight of component (D).

3. The additive formulation according to claim 1, in which component (A) is a copolymer of sulfur dioxide with one or more linear or branched 1-olefins having from 2 to 24 carbon atoms.

4. The additive formulation according to claim 1, in which component (A) has a number-average molecular weight M.sub.n of from 2000 to 1 000 000.

5. The additive formulation according to claim 1, in which component (A) comprises less than 15 mol % of olefin not converted in the copolymerization with the sulfur dioxide.

6. The additive formulation according to claim 1, in which component (B) is an -olefin-maleimide copolymer having at least one basic nitrogen atom.

7. The additive formulation according to claim 6, in which component (B) is obtainable by free-radical polymerization of one or more linear or branched -olefins having from 6 to 50 carbon atoms with maleic anhydride and subsequent reaction with one or more aliphatic polyamines.

8. The additive formulation according to claim 6, in which component (B) has a weight-average molecular weight M.sub.w of from 500 to 50 000.

9. The additive formulation according to claim 1, in which component (C) is an organic sulfonic acid which has a hydrocarbyl radical having from 6 to 40 carbon atoms.

10. The additive formulation according to claim 1, in which the aromatic hydrocarbon mixture of component (D) are compounds having from 9 to 14 carbon atoms.

11. A process for preparing the additive formulation according to claim 1, which comprises first mixing components (A) and (C) homogeneously with one another in the presence of at least a portion of the high-boiling organic solvent (D), and then incorporating component (B).

12. An antistatically modified inanimate organic material comprising from 0.01 to 2000 ppm by weight of the additive formulation according to claim 1, wherein the inanimate organic material is selected from the group consisting of cosmetic preparations, medicament formulations, photographic recording materials, paints and varnishes, plastics, waxes, solvents, mineral oil products and fuels.

Description

EXAMPLE 1

Preparation of a 1-decene-sulfur dioxide Copolymer at 25 C.

(1) A 5 liter autoclave was initially charged with 1122 g (7.90 mol) of 1-decene and 28 g of dodecyl mercaptan in 350 g of Solvent Naphtha Heavy (Solvesso 150). At from 10 to 20 C., 950 g (14.84 mol) of sulfur dioxide were introduced. Thereafter, the reaction mixture was adjusted to 25 C., and a solution of 72 g of tert-butyl peroxypivalate (75% strength by weight) in 700 g of Solvent Naphtha Heavy was introduced at this temperature over 3 hours. Subsequently, the mixture was stirred at 20 C. for a further 5 hours For workup, the autoclave was decompressed and degassing was effected first at standard pressure and then under reduced pressure (from 200 to 10 mbar). 2.4 kg of a clear viscous polymer solution were obtained. The conversion was 95% (determined by .sup.1H NMR spectroscopy on the basis of the integral ratio of the 3 olefin protons of the residue olefin at 5.8 ppm/4.9 ppm to the 3 protons in the main polymer chain at 4.3-3.0 ppm). The 1-decene-sulfur dioxide copolymer thus obtained had a number-average molecular weight M.sub.n of 19600 and a polydispersity PDI of 3.2.

EXAMPLE 2

Preparation of a 1-decene-sulfur dioxide Copolymer at 35 C.

(2) A 5 liter autoclave was initially charged with 1122 g (7.90 mol) of 1-decene and 28 g of dodecyl mercaptan in 350 g of Solvent Naphtha Heavy (Solvesso 150). At from 10 to 20 C., 950 g (14.84 mol) of sulfur dioxide were introduced. Thereafter, the reaction mixture was adjusted to 35 C., and a solution of 72 g of tert-butyl peroxypivalate (75% strength by weight) in 700 g of Solvent Naphtha Heavy was introduced at this temperature over 2 hours. Subsequently, the mixture was stirred at 20 C. for a further 4 hours. For workup, the autoclave was decompressed, and degassing was effected first at standard pressure and then under reduced pressure (from 200 to 10 mbar). 2.5 kg of a clear viscous polymer solution were obtained. The conversion was 97% (determined by .sup.1H NMR spectroscopy on the basis of the integral ratio of the 3 olefin protons of the residue olefin at 5.8 ppm/4.9 ppm to the 3 protons in the main polymer chain at 4.3-3.0 ppm). The 1-decene-sulfur dioxide copolymer thus obtained had a number-average molecular weight M.sub.n of 13400 and a polydispersity PDI of 2.9.

EXAMPLE 3

Preparation of a 1-decene-sulfur dioxide Copolymer at 33 C.

(3) A 5 liter autoclave was initially charged with 1122 g (7.90 mol) of 1-decene and 28 g of dodecyl mercaptan in 630 g of Solvent Naphtha Heavy (Solvesso 150). At from 10 to 20 C., 720 g (11.25 moll of sulfur dioxide were introduced. Thereafter, the reaction mixture was adjusted to 33 C., and a solution of 88 g of tert-butyl peroxypivalate (75% strength by weight) in 420 g of Solvent Naphtha Heavy was introduced at this temperature over 2 hours. Subsequently, the mixture was stirred at 20 C. for a further 4 hours. For workup, the autoclave was decompressed, and degassing was effected first at standard pressure and then under reduced pressure (from 200 to 10 mbar). 2.5 kg of a clear viscous polymer solution were obtained. The conversion was 92% (determined by .sup.1H NMR spectroscopy on the basis of the integral ratio of the 3 olefin protons of the residue olefin at 5.8 ppm/4.9 ppm to the 3 protons in the main polymer chain at 4.3-3.0 ppm). The 1-decene-sulfur dioxide copolymer thus obtained had a number-average molecular weight M.sub.n of 12500 and a polydispersity PDI of 2.5.

EXAMPLE 4

Preparation of an Additive Formulation from a 1-decene-sulfur dioxide Copolymer, a C20/24-olefin-maleimide Copolymer, Dodecylbenzenesulfonic Acid and Solvent Naphtha Heavy

(4) 1 kg of the 1-decene-sulfur dioxide copolymer solution (50% strength by weight in Solvent Naphtha Heavy) from example 2 [component (A)] was mixed with a further 1.1 kg of Solvent Naphtha Heavy at from 25 to 35 C. with stirring. Thereafter, 160 g of dodecylbenzenesulfonic acid [component (C)] were added at the same temperature with stirring and mixed homogeneously. This mixture was stirred at from 40 to 50 C. for 10 minutes. Subsequently 1 kg of a solution of C.sub.20/24-olefin-maleic anhydride copolymer which had been converted to the imide with tallow fat-1,3-diaminopropane and had a weight-average molecular weight M.sub.w in the range from 2000 to 5000 [component (B)] in Solvent Naphtha Heavy (50% strength by weight) was added at a temperature of from 40 to 50 C. and mixed homogeneously. The resulting additive formulation had a composition of 15.3% by weight of (A), 15.3% by weight of (B), 4.9% by weight of (C) and 64.4% by weight of Solvent Naphtha Heavy [component (D)].

EXAMPLE 5

Preparation of an Additive Formulation from a 1-decene-sulfur dioxide Copolymer, a C20/24-olefin-maleimide Copolymer, Dodecylbenzenesulfonic Acid and Solvent Naphtha Heavy

(5) The same components (A), (B), (C) and (D) were mixed in analogy to the formulation in example 4 in such ratios as to result in an additive formulation of the composition of 21% by weight of (A), 18% by weight of (B). 7% by weight of (C) and 54% by weight of (D).

EXAMPLE 6

Preparation of an Additive Formulation from a 1-decene-sulfur dioxide Copolymer, a C20/24-olefin-maleimide Copolymer, Dodecylbenzenesulfonic Acid and Solvent Naphtha Heavy

(6) The same components (A), (B), (C) and (D) were mixed in analogy to the formulation in example 4 in such ratios as to result in an additive formulation of the composition of 14% by weight of (A), 13% by weight of (B), 5% by weight of (C) and 68% by weight of (D).

EXAMPLE 7 (for Comparison)

Preparation of an Additive Formulation from a 1-decene-sulfur dioxide Copolymer, an N-tallowfatamine/1,3-diaminopropane-epichlorohydrin Reaction Product, Dodecylbenzenesulfonic Acid and Solvent Naphtha Heavy

(7) A formulation analogous in the ratios of the four components to the formulation of example 6 was prepared, with the only difference that, instead of the 50% by weight C.sub.20/24-Olefin-maleimide copolymer solution, the same amount of a commercially available 50% by weight solution of the polymeric condensation product of N-tallow-fatamine-1,3-diaminopropane and epichlorhydrin in a mixture of aromatic hydrocarbonsaccording to the teaching of document (1)was used.

EXAMPLE 8

Measurement of the Conductivities of the Additive Formulations

(8) Measurements of the electrical conductivity were carried out to DIN standard 51412-2 (field method). To this end, an immersion test cell was immersed into the liquids to be analyzed. The conductivity values in pS/m were each read off on the display of the immersion test cell at the same temperature of the liquids, specifically 25 C. The liquids to be analyzed were commercial petroleum, commercial diesel fuel, commercial heating oil, commercial turbine fuel and commercial hydraulic oil, into which a particular amount of the additive formulation had in each case been added as a conductivity improver beforehand. The overview which follows shows the results of the measurements. a) n commercial petroleum (dosage: in each case 3 mg per liter): the additive formulation from example 5 (inventive) gave 890 pS/m; the additive formulation from example 6 (inventive) gave 750 pS/m; the additive formulation from example 7 (for comparison) gave 540 pS/m; a commercial antistat formulation (AF1) gave 760 pS/m; b) in commercial diesel fuel (dosage: in each case 3 mg per liter): the additive formulation from example 5 (inventive) gave 670 pS/m; the additive formulation from example 6 (inventive) gave 440 pS/m; a commercial antistat formulation (AF1) gave 415 pS/m; c) in commercial heating oil (dosage: in each case 3 mg per liter): the additive formulation from example 5 (inventive) gave 690 pS/m; the additive formulation from example 6 (inventive) gave 520 pS/m; a commercial antistat formulation (AF1) gave 505 pS/m; d) in commercial turbine fuel (dosage: in each case 1, 3 or 5 mg per liter): the additive formulation from example 5 (inventive) gave 174 pS/m at 1 mg per liter, 750 pS/m at 3 mg per liter, and 1275 pS/m at 5 mg per liter; after 4 days of storage time in each case, the conductivity measurements were repeated and gave values of 230 pS/m (at 1 mp per liter), 735 pS/m (at 3 mg per liter) and 1205 pS/m (at 5 mg per liter); a commercial antistat formulation (AF2) gave 205 pS/m at 1 mg per liter, 723 pS/m at 3 mg per liter, and 1230 pS/m at 5 mg per liter; after 4 days of storage time in each case, the conductivity measurements were repeated and gave values of 150 pS/m (at 1 mg per liter), 677 pS/m (at 3 mg per liter) and 1034 pS/m (at 5 mg per liter); e) in commercial hydraulic oil (dosage in each case 130 mg per liter): the additive formulation from example 5 (inventive) gave 167 pS/m; a commercial antistat formulation (AF1) gave 120 pS/m.

(9) For the commercial antistat formulations for improving the electrical conductivity in organic liquids (AF1 and AF2), a composition according to the teaching of document (1) is adopted.

(10) The test results show that the inventive additive formulations are at least on a par with the corresponding prior art additive formulationswithin the precision of measurement of, as experience has shown, approx. 10-20 pS/m; in most cases, however, they surpass them and afford the desired significantly higher electrical conductivities, especially also in direct comparison with comparative example 7. This is also true of inventive example 6, which has a comparatively high content of solvent (D), i.e. is relatively highly diluted, but nevertheless affords the sufficiently high electrical conductivities as are also achieved with a commercial antistat formulation. In the measurements in the turbine fuel, as a further advantage of the inventive additive formulation, it should be noted that the electrical conductivity of the turbine fuel, even after a certain storage time, remains constant at the high levelunlike the turbine fuel treated with commercial antistat formulation, whose conductivity declines significantly after said storage time.

EXAMPLE 9

Examination of Storage Stability and Flashpoint of Additive Formulations

(11) The storage stabilities of the inventive additive formulations from example 5 and 6 and of commercial antistat formulations (AF1 and AF2) were after prolonged storage at a constant 40 C., assessed for cloudiness and possible formation of precipitates by visual examination. In all cases, the samples had no cloudiness or precipitates after 3 months of storage. The flashpoints of the samples used had been determined beforehand to the EN ISO standard 2719:2002 (measurement in a closed crucible according to Pensky-Martens): in the case of the inventive samples, they were 62 C. (example 5) and 63 C. (example 6), but significantly lower for the commercial antistat formulation at 21 C. (AF1) and <20 C. (AF2).